CN110452082A - It is the method and device that raw material produces diisobutylene to mix carbon four - Google Patents

It is the method and device that raw material produces diisobutylene to mix carbon four Download PDF

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Publication number
CN110452082A
CN110452082A CN201910717699.6A CN201910717699A CN110452082A CN 110452082 A CN110452082 A CN 110452082A CN 201910717699 A CN201910717699 A CN 201910717699A CN 110452082 A CN110452082 A CN 110452082A
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carbon
reaction
discharge port
reactor
feed inlet
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CN110452082B (en
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***
吕晓东
孙方宪
周璇
段宏毅
温世昌
何红梅
李倞琛
赵霞
赵龙
于海霞
陈瑞
徐冲
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China National Petroleum Corp
CNPC EastChina Design Institute Co Ltd
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China National Petroleum Corp
CNPC EastChina Design Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C07C2531/08—Ion-exchange resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

It is the method and device that raw material produces diisobutylene that the invention discloses a kind of to mix carbon four, belongs to technical field of petrochemical industry.The device provided in an embodiment of the present invention that diisobutylene is produced to mix carbon four as raw material, including shell journey superposition reactor, catalytic distillation tower and recovery tower；When producing diisobutylene, the first reaction mass is inputted by first charging aperture, the first reaction mass includes that the first mixing carbon four, second mixes carbon four and inhibitor, and by the 9th discharge port output reaction product, which mainly includes diisobutylene.The device mainly passes through a reactor and two tower production diisobutylene, reduces equipment used in production diisobutylene, reduces occupied area, reduce production cost and investment.

Description

It is the method and device that raw material produces diisobutylene to mix carbon four
Technical field
The present invention relates to technical field of petrochemical industry.In particular to a kind of to produce diisobutylene to mix carbon four as raw material Method and device.
Background technique
Isobutene is a kind of important industrial chemicals, be mainly used for synthesizing MTBE (Methyl Tert-Butyl Ether, Methyl tertiary butyl ether(MTBE)).MTBE is commonly used for gasoline additive due to octane number with higher at present.Also, the antidetonation of MTBE is quick-fried Property is good.But national correlation department provides, future will promote the use of ethanol petrol, and in ethanol petrol in addition to ethyl alcohol, other are organic to contain Oxygen compound content is no more than 0.5% and must not artificially be added, and therefore, MTBE will no longer be added as organic oxygen-containing compound It adds in gasoline.In this case, the outlet of isobutene becomes industry focus of attention.It has been investigated that isobutene can lead to It crosses dimerization reaction and generates dimer diisobutylene, diisobutylene is not organic oxygen-containing compound, and can be added directly as gasoline Add agent, or diisobutylene is hydrogenated to isooctane, using isooctane as gasoline additive.And how to be synthesized by isobutene Diisobutylene becomes the problem of people's urgent need to resolve.
It is mainly raw material by the way that inhibitor synthesis is added to mix carbon four in the relevant technologies such as CN201711235599.7 Diisobutylene, mixing carbon four be the hydrocarbon mixture containing four carbon atom, except include isobutene in addition to, further include other hydro carbons such as 1- butylene, 2- butylene etc..It mainly include in the related technology catalytic distillation to mix the device that carbon four is raw material production diisobutylene Tower, extraction tower, recovery tower and two reactors.Wherein, first reactor is connected with catalytic distillation tower, catalytic distillation tower respectively with Second reactor is connected with extraction tower, and extraction tower is connected with recovery tower.Mixing carbon four and inhibitor enter first reactor, finally Dimer diisobutylene is exported by extraction tower.
But in the related technology with mix carbon four be raw material produce diisobutylene device used in equipment it is more, occupied area It is larger, lead to high production cost, investment is big.
Summary of the invention
It is the method and device that raw material produces diisobutylene that the embodiment of the invention provides a kind of to mix carbon four, can be solved Certainly more to mix the device device therefor that carbon four is raw material production diisobutylene, high production cost puts into big problem.Specifically Technical solution is as follows:
On the one hand, it is the device that raw material produces diisobutylene that the embodiment of the invention provides a kind of to mix carbon four, described Device includes: shell journey superposition reactor, catalytic distillation tower, recovery tower；
The shell journey superposition reactor includes tube side reactor and shell side reactor, and the tube side reactor is located at described In shell side reactor；
The middle and upper part of shell side reactor side is equipped with first charging aperture, and the bottom of the tube side reactor is equipped with second Feed inlet, the middle and upper part of the shell side reactor other side are equipped with the first discharge port, in the shell side reactor other side under Portion is equipped with the second discharge port, and the top of the tube side reactor is equipped with third discharge port, the second charging aperture and described second Discharge port connection；
The middle and lower part of the catalytic distillation tower side is equipped with third feed inlet and the 4th feed inlet, and the catalytic distillation tower is another The lower part of side is equipped with the 5th feed inlet, and the top of the catalytic distillation tower other side is equipped with the 6th feed inlet, and the catalysis is steamed The top for evaporating tower is equipped with the 4th discharge port, and the bottom of the catalytic distillation tower is equipped with the 5th discharge port and the 6th discharge port；It is described 4th discharge port is connect with the first charging aperture, the second charging aperture and the 6th feed inlet respectively, the described 5th into Material mouth is connected with the 5th discharge port；First discharge port is connected with the 4th feed inlet, the third feed inlet and The third discharge port connection；
The middle and lower part of the recovery tower side is equipped with the 7th feed inlet, and the middle and lower part of the recovery tower other side is equipped with the 8th Feed inlet, the middle and upper part of the recovery tower other side are equipped with the 9th feed inlet, and the top of the recovery tower is equipped with the 7th discharge port, The bottom of the recovery tower is equipped with the 8th discharge port and the 9th discharge port；7th feed inlet and the 6th discharge port connect Connect, the 8th feed inlet is connected with the 8th discharge port, the 7th discharge port respectively with the first charging aperture and institute State the connection of the 9th feed inlet；
The first charging aperture is used for output-response product, institute for inputting the first reaction mass, the 9th discharge port It mainly includes two different that the first reaction mass, which is stated, including the first mixing carbon four, second mixing carbon four and inhibitor, the reaction product Butylene.
In one possible implementation, described device further include: feed preheater and product cooler；
One end of the feed preheater is connected with the first charging aperture, the other end of the feed preheater and first Input channel connection；First input channel is used for for inputting first reaction mass, the feed preheater to institute State the heating of the first mixing carbon four；
One end of the product cooler is connected with the 9th discharge port, the other end and first of the product cooler Output channel connection；First output channel is for exporting the reaction product.
In alternatively possible implementation, described device further include: shell side cooler and shell side booster；
One end of the shell side booster is connected with second discharge port, the other end of the shell side booster and described One end of shell side cooler connects；
The other end of the shell side cooler is connected with the second charging aperture.
In alternatively possible implementation, described device further include: the first reboiler and the second reboiler；
One end of first reboiler is connected with the 5th feed inlet, the other end of first reboiler and described The connection of 5th discharge port；
One end of second reboiler is connected with the 8th feed inlet, the other end of second reboiler and described The connection of 8th discharge port.
In alternatively possible implementation, described device further include: the first condenser, the second condenser, first time Flow pump, the second reflux pump, the first return tank and the second return tank；
One end of first condenser is connected with the 4th discharge port, the other end of first condenser and described One end of first return tank connects, and the other end of first return tank is connected with one end of first reflux pump, and described the The other end of one reflux pump is exported with the first charging aperture, the second charging aperture, the 6th feed inlet and second respectively Pipeline connection；
One end of second condenser is connected with the 7th discharge port, the other end of second condenser and described One end of second return tank connects, and the other end of second return tank is connected with one end of second reflux pump, and described the The other end of two reflux pumps is connect with the first charging aperture and the 9th feed inlet respectively；
Wherein, the other end of first reflux pump is connected by the first regulating valve with the first charging aperture；
The other end of first reflux pump is connected by second regulating valve with the second charging aperture；
First regulating valve is used to adjust the inlet amount into the second mixing carbon four in the first charging aperture；
Second regulating valve is used to adjust the inlet amount into third mixing carbon four in the second charging aperture；
The second mixing carbon four is to convey through first condenser, first return tank and first reflux pump To the mixing carbon four of the first charging aperture；
The third mixing carbon four is defeated through first condenser, first return tank warp and first reflux pump It send to the mixing carbon four of the second charging aperture；
Second output channel is for exporting remaining mixing four product of carbon.
In alternatively possible implementation, the first catalyst is filled in the shell side reactor；
The tube side reactor includes multiple reaction tubes, and the multiple reaction tube is triangular in shape in the tube side reactor Arrangement, the distance between die of two neighboring reaction tube are 100~500mm；
For each reaction tube, the height of the reaction tube is 1000~15000mm, the diameter of the reaction tube is 50~ 250mm is filled with the second catalyst in the reaction tube；
The both ends of the reaction tube are equipped with sieve, and the screen slot size of the sieve is less than the grain of second catalyst granules Diameter；The corresponding circulation area of the screen slot of the sieve is not less than twice of the corresponding cross-sectional area of outlet of the reaction tube.
In alternatively possible implementation, the catalytic distillation tower includes the first rectifying section, the first conversion zone and the One stripping section；
First rectifying section includes 15~25 blocks of column plates, and first stripping section includes 25~35 blocks of column plates；
The recovery tower includes the second rectifying section and the second stripping section；
Second rectifying section includes 10~15 blocks of column plates, and second stripping section includes 20~30 blocks of column plates.
On the other hand, it is the method that raw material produces diisobutylene, institute that the embodiment of the invention provides a kind of to mix carbon four The method of stating includes:
First reaction mass is delivered to the shell side reactor in shell journey superposition reactor, first reaction mass exists Dimerization reaction occurs under the conditions of first catalyst is existing, obtains the first mixture；First reaction mass includes first mixed It closes carbon four, second and mixes carbon four and inhibitor；It include reaction product and the inhibitor in first mixture；The reaction It mainly include diisobutylene in product；
Second reaction mass is delivered to the tube side reactor in the shell journey superposition reactor, second reactant Dimerization reaction occurs under the conditions of material is existing for the second catalyst, obtains the second mixture, second reaction mass includes institute The first mixture and third mixing carbon four are stated, second mixture includes that the reaction product, the inhibitor and the 4th are mixed Carbon four is closed, the 4th mixing carbon four is second reaction mass unreacted mixing carbon four in the tube side reactor；
Respectively by second mixture from third discharge port through third feed inlet, first reaction mass in the shell Unreacted gas phase mixing the first discharge port of carbon four selfs that journey reactor is generated by vaporization is delivered to catalysis through the 4th feed inlet In destilling tower, first reaction mass mixes carbon four and institute in the unreacted gas phase that shell side reactor is generated by vaporization It states the 4th mixing carbon four and dimerization reaction occurs in the catalytic distillation tower, obtain third mixture, the third mixture packet The reaction product, inhibitor and the 5th mixing carbon four are included, the 5th mixing carbon four is first through the catalytic distillation tower The unreacted mixing carbon four of conversion zone；
Reaction product and inhibitor in the third mixture mix carbon with the described 5th in the catalytic distillation tower Four separation, by the third mixture after separation reaction product and the inhibitor be delivered to recovery tower；The reaction Product and the inhibitor separate in the recovery tower, and the reaction product makes as output of products, the inhibitor circulation With and being delivered to the shell as first reaction mass after described first mixes carbon four and the second mixing carbon four mixes Journey reactor.
In one possible implementation, the method also includes:
The 5th mixing carbon four is divided for four part mixing carbon four, first part's mixing carbon four is back to the catalysis steaming It evaporates in tower, second part mixing carbon four is delivered to the shell side reactor, Part III mixing as the second mixing carbon four Carbon four mixes carbon four as the third, is delivered to the tube side reactor, Part IV mixing carbon four is as remaining mixing carbon Four output of products.
In alternatively possible implementation, it is described respectively by second mixture from third discharge port through third into Gas phase mixing the first discharge port of carbon four selfs warp that material mouth, first reaction mass are generated in the shell side reactor by vaporization 4th feed inlet is delivered in catalytic distillation tower, comprising:
Second mixture is delivered to the catalytic distillation tower through the third feed inlet from the third discharge port 4th~10 block of column plate of the first stripping section；
First reaction mass is mixed into carbon four in the unreacted gas phase that the shell side reactor is generated by vaporization The 6th~12 piece of tower of first stripping section of catalytic distillation tower is delivered to through the 4th feed inlet from first discharge port Plate.
In alternatively possible implementation, the reaction pressure in the shell side reactor is 0.5~0.9MPa, reaction Temperature is 70~90 DEG C, and air speed of first catalyst in the shell side reactor is 0.5~1h-1；
Reaction pressure in the tube side reactor is 1.5~2.5MPa, and reaction temperature is no more than 120 DEG C, described second Air speed of the catalyst in the tube side reactor is 1~3h-1, and the loadings of second catalyst are tube side reaction The 65%~85% of body product；
The first conversion zone air speed is 1~3h in the catalytic distillation tower-1, reaction temperature is 60~80 DEG C, and reaction pressure is 0.6~1.0MPa；
In the recovery tower tower top temperature be 60~90 DEG C, column bottom temperature be 160~190 DEG C, operating pressure be 0.5~ 1.0MPa。
In alternatively possible implementation, the molar ratio of isobutene in the inhibitor and the first mixing carbon four For 0.01~0.1:1；
The inhibitor is the tert-butyl alcohol.
In alternatively possible implementation, the quality of the second mixing carbon four is described the in first reaction mass The 15%~75% of one mixing four mass of carbon；
In second reaction mass third mixing carbon four quality be it is described first mixing four mass of carbon 15%~ 75%.
Technical solution provided in an embodiment of the present invention has the benefit that
The device provided in an embodiment of the present invention that diisobutylene is produced to mix carbon four as raw material, including shell journey overlapping are anti- Answer device, catalytic distillation tower and recovery tower；When producing diisobutylene, by first charging aperture input the first reaction mass, first Reaction mass includes that the first mixing carbon four, second mixes carbon four and inhibitor, and by the 9th discharge port output reaction product, this is anti- Answering product mainly includes diisobutylene.The device mainly passes through a reactor and two tower production diisobutylene, reduces Equipment used in diisobutylene is produced, reduces occupied area, reduces production cost and investment.
Detailed description of the invention
Fig. 1 is provided in an embodiment of the present invention a kind of to mix the signal that carbon four is the device that raw material produces diisobutylene Figure；
Fig. 2 is provided in an embodiment of the present invention another to mix the signal that carbon four is the device that raw material produces diisobutylene Figure；
Fig. 3 is provided in an embodiment of the present invention a kind of to mix the process that carbon four is the method that raw material produces diisobutylene Figure.
Appended drawing reference respectively indicates:
10- shell journey superposition reactor, 11- tube side reactor, 12- shell side reactor, 20- catalytic distillation tower,
30- recovery tower, 101- first charging aperture, 102- second charging aperture, the first discharge port of 103-,
The second discharge port of 104-, 105- third discharge port, 106- third feed inlet, the 4th feed inlet of 107-,
The 5th feed inlet of 108-, the 6th feed inlet of 109-, the 4th discharge port of 110-, the 5th discharge port of 111-,
The 6th discharge port of 112-, the 7th feed inlet of 113-, the 8th feed inlet of 114-, the 9th feed inlet of 115-,
The 7th discharge port of 116-, the 8th discharge port of 117-, the 9th discharge port of 118-, 40- feed preheater,
50- product cooler, 60- shell side cooler, 70- shell side booster, the first reboiler of 80-,
The second reboiler of 90-, the first condenser of 201-, the second condenser of 202-, the first reflux pump of 203-,
The second reflux pump of 204-, the first return tank of 205-, the second return tank of 206-, the first regulating valve of 207-,
The second regulating valve of 208-.
Specific embodiment
To keep technical solution of the present invention and advantage clearer, embodiment of the present invention is made below further detailed Description.
It is the device that raw material produces diisobutylene that the embodiment of the invention provides a kind of to mix carbon four, referring to Fig. 1, the dress Set includes: shell journey superposition reactor 10, catalytic distillation tower 20 and recovery tower 30；
Shell journey superposition reactor 10 includes tube side reactor 11 and shell side reactor 12, and tube side reactor 11 is located at shell side In reactor 12；
The middle and upper part of 12 side of shell side reactor is equipped with first charging aperture 101, and the bottom of tube side reactor 11 is equipped with second Feed inlet 102, the middle and upper part of 12 other side of shell side reactor are equipped with the first discharge port 103, in 12 other side of shell side reactor Lower part is equipped with the second discharge port 104, and the top of tube side reactor 11 is equipped with third discharge port 105, second charging aperture 102 and second Discharge port 104 connects；
The middle and lower part of 20 side of catalytic distillation tower is equipped with third feed inlet 106 and the 4th feed inlet 107, catalytic distillation tower 20 The lower part of the other side is equipped with the 5th feed inlet 108, and the top of 20 other side of catalytic distillation tower is equipped with the 6th feed inlet 109, catalysis The top of destilling tower 20 is equipped with the 4th discharge port 110, and the bottom of catalytic distillation tower 20 is equipped with the 5th discharge port 111 and the 6th discharging Mouth 112；4th discharge port 110 is connect with first charging aperture 101, second charging aperture 102 and the 6th feed inlet 109 respectively, and the 5th Feed inlet 108 and the connection of the 5th discharge port 111；First discharge port 103 and the connection of the 4th feed inlet 107,106 He of third feed inlet Third discharge port 105 connects；
The middle and lower part of 30 side of recovery tower is equipped with the 7th feed inlet 113, and the middle and lower part of 30 other side of recovery tower is equipped with the 8th Feed inlet 114, the middle and upper part of 30 other side of recovery tower are equipped with the 9th feed inlet 115, and the top of recovery tower 30 is equipped with the 7th discharging The bottom of mouth 116, recovery tower 30 is equipped with the 8th discharge port 117 and the 9th discharge port 118；7th feed inlet 113 and the 6th discharging Mouthfuls 112 connect, the 8th feed inlet 114 and the connection of the 8th discharge port 117, the 7th discharge port 116 respectively with first charging aperture 101 and The connection of 9th feed inlet 115；
First charging aperture 101 is used to export and the uncle in mixture for inputting the first reaction mass, the 9th discharge port 118 The reaction product of butanol separation, the first reaction mass include that the first mixing carbon four, second mixes carbon four and inhibitor, reaction product It mainly include diisobutylene.
Wherein, shell side reactor 12 and tube side reactor 11 generate reaction product for isobutene generation dimerization reaction.It urges Change destilling tower 20 to be used to separate reaction product and inhibitor with mixing carbon four.First discharge port 103 is for exporting the first reaction The unreacted gas phase first that material is generated by vaporization mixes carbon four and unreacted gas phase second mixes the mixture of carbon four, For 4th feed inlet 107 for inputting unreacted gas phase mixing carbon four, which includes unreacted Gas phase first mixes carbon four and unreacted gas phase second mixes carbon four, and the second discharge port 104 is for exporting shell side reactor 12 It is middle to react obtained reaction product, second charging aperture 102 be used to input the reaction product reacted in shell side reactor 12 and Third mixes carbon four, i.e. the second reaction mass, and third discharge port 105 includes for exporting the second mixture, the second mixture The reaction product reacted in four mixing carbon four, inhibitor and tube side reactor 11, the 4th mixing carbon four is the second reactant Material unreacted mixing carbon four in tube side reactor, it is mixed that third feed inlet 106 is used for the input second into catalytic distillation tower 20 Close object.
4th discharge port 110 for export the 5th mixing carbon four, the 5th mixing carbon four be through catalytic distillation tower conversion zone not The mixing carbon four of reaction, the 5th discharge port 111 are used for the mixture of output-response product and the tert-butyl alcohol, and the 5th feed inlet 108 is used It is recycled in catalytic distillation tower 20 in the mixture for exporting the 5th discharge port 111, the 6th discharge port 112 is produced for output-response The mixture of object and inhibitor, reaction product and inhibitor of the 7th feed inlet 113 for exporting the 6th discharge port 112 are mixed It closes object to be input in recovery tower 30, recovery tower 30 is used for the reaction product and inhibitor separation in mixture.
5th mixing carbon four is through the unreacted mixing carbon four of catalytic distillation tower conversion zone, and the 5th mixing carbon four can be divided into Four part mixing carbon four, first part's mixing carbon four are back in catalytic distillation tower, and second part mixing carbon four is mixed as second Carbon four is closed, shell side reactor is delivered to, Part III mixing carbon four mixes carbon four as third, is delivered to tube side reactor, the Four part mixing carbon four are as remaining mixing four output of products of carbon.
The first part that 6th feed inlet 109 is used to mix in carbon four by the 5th mixes carbon four and is back to catalytic distillation tower 20 In, the 7th discharge port 116 for export the tert-butyl alcohol separated with diisobutylene, diisobutylene that the 8th discharge port 117 exports and The mixture of a small amount of tert-butyl alcohol is liquid phase, is returned back after the second reboiler 90 is heated to be gas-liquid two-phase through the 8th feed inlet 114 Receive tower 30.9th feed inlet 115 is for a part of tert-butyl alcohol separated with diisobutylene to be back in recovery tower 30.First is mixed Closing in carbon four and the second mixing carbon four includes not only isobutene, further includes other hydro carbons such as 1- butylene, 2- butylene etc..Wherein, The mixing carbon four that one mixing carbon four can generate for steam cracking, or the mixing carbon four that catalytic cracking generates.In this hair In bright embodiment, this is not especially limited.
It should be noted is that diisobutylene easily forms azeotropic mixture with the tert-butyl alcohol, if directly by diisobutylene and uncle The azeotropic mixture of butanol causes the diisobutylene purity generated lower as output of products.Also, GB18351 " vehicle-use alcohol gasoline (E10) " provide that in ethanol petrol in addition to ethyl alcohol, other are organic with GB 22030 " vehicle-use alcohol gasoline blending component oil " standard Oxygenates level is no more than 0.5% and must not artificially be added, and the tert-butyl alcohol belongs to organic oxygen-containing compound, not directly adds It is added in gasoline, therefore, diisobutylene should be separated with the tert-butyl alcohol.
In embodiments of the present invention, the device of the production diisobutylene provided through the embodiment of the present invention will be steamed from catalysis The diisobutylene of the 6th discharge port 112 output and the mixture of the tert-butyl alcohol for evaporating tower 20 are input in recovery tower 30, in recovery tower The mixture is separated in 30, wherein diisobutylene is exported as product from the tower bottom of recovery tower 30, and the tert-butyl alcohol is from recovery tower 30 Tower top output, wherein a part of tert-butyl alcohol with first mix carbon four and second mixing carbon four mixing after be used as the first reactant Material is recycled, and a part of tert-butyl alcohol is back in recovery tower 30.To realize the separation of diisobutylene and the tert-butyl alcohol, improve The purity of diisobutylene.
In addition, at least needing two reactors in the relevant technologies CN201711235599.7 when producing diisobutylene.And In embodiments of the present invention, shell side reactor 12 and tube side reactor 11 are integrated into a reactor, i.e. shell journey overlapping is anti- Device 10 is answered, so as to reduce the occupied area of equipment, reduces production cost and investment.
In one possible implementation, the position of inlet port and outlet port, which can according to need, is selected simultaneously more Change, the size of inlet port and outlet port, which also can according to need, to be selected and changed, and in embodiments of the present invention, is not made to this It is specific to limit.
The device provided in an embodiment of the present invention that diisobutylene is produced to mix carbon four as raw material, including shell journey overlapping are anti- Answer device 10, catalytic distillation tower 20 and recovery tower 30；When producing diisobutylene, pass through first reaction of the input of first charging aperture 101 Material, the first reaction mass include that the first mixing carbon four, second mixes carbon four and inhibitor, are exported by the 9th discharge port 118 Reaction product, the reaction product mainly include diisobutylene.The device mainly passes through a reactor and two tower productions two Isobutene reduces equipment used in production diisobutylene, reduces occupied area, reduce production cost and investment.
In one possible implementation, referring to fig. 2, which further includes feed preheater 40 and product cooler 50；
One end of feed preheater 40 and first charging aperture 101 connect, the other end of feed preheater 40 and the first input Pipeline connection；First input channel is used to heat the first mixing carbon four for inputting the first reaction mass, feed preheater 40；
One end of product cooler 50 and the connection of the 9th discharge port 118, the other end of product cooler 50 and the first output Pipeline connection；First output channel is used for output-response product.
In embodiments of the present invention, the first mixing carbon four passes through feed preheater 40 before entering shell side reactor 12 Heating, the first mixing carbon four after heating are entered in shell side reactor 12 by the first input channel, are filled in shell side reactor 12 It is filled with the first catalyst, the first reaction mass reacts under the catalytic action of the first catalyst.Wherein, the first mixing carbon four For from the externally input reaction mass of the device, the second mixing carbon four and inhibitor are the reactant that the device recycles Material.
Product cooler 50 is for cooling down reaction product, and the first output channel is for exporting reaction product after cooling.
It should be noted is that the reaction that isobutene generates diisobutylene is exothermic reaction, therefore, in reaction process In, by the pressure in control shell side reactor 12, the first reaction mass is made to react under the boiling point of relevant pressure, reacted Heat makes the first reaction mass in gas-liquid mixture phase, and part first mixes carbon four and part second mixes vapour due to reaction heat of carbon four Change, unreacted gas phase mixes carbon four and enters catalysis by the 4th feed inlet 107 of catalytic distillation tower 20 from the first discharge port 103 In destilling tower 20.Unreacted gas phase mixing carbon four includes the unreacted gas phase vaporized in the first reaction mass by reaction heat First mixing carbon four and unreacted gas phase second mix carbon four.Since reaction heat is used for the vaporization of the first reaction mass, shell side Reaction temperature is held essentially constant in reactor, without individually setting circulation takes thermal outside shell side reactor 12； And the reaction heat of the second reaction mass in tube side reactor 11 is also by the vaporization institute of the first reaction mass in shell side reactor 12 It absorbs, does not also need individually to be arranged to recycle outside tube side reactor 11 to take thermal；Thus eliminating the need the relevant technologies as applied Circulation is set outside fixed bed reactors in (patent) number CN201711235599.7 and takes thermal, the reaction product of circulation is through outside Returning reactor entrance causes dimer concentration increase in the reactor after cooler is cooling, and increases with bipolymer concentration, The drawbacks of by-product trimer, tetramer increase can increase substantially the utilization rate of the first catalyst, the second catalyst bed, It can reduce by the first catalyst amount 30%~40% compared with fixed bed reactors device.
In one possible implementation, device further include: shell side cooler 60 and shell side booster 70；
One end of shell side booster 70 and the connection of the second discharge port 104, the other end and shell side of shell side booster 70 are cooling One end of device 60 connects；
The other end and second charging aperture 102 of shell side cooler 60 connect.
In one possible implementation, the temperature and pressure in shell side reactor 12 and the temperature in tube side reactor 11 It spends different with pressure.Therefore, the first mixture can pass through shell side booster 70 and shell before entering in tube side reactor 11 Journey cooler 60 is boosted and is cooled down.
Shell side booster 70 is used for the pressure rise of the first mixture to the first preset pressure, and shell side cooler 60 is used for The temperature of first mixture is cooled to the first preset temperature.
In one possible implementation, device further include: the first reboiler 80 and the second reboiler 90；
One end of first reboiler 80 and the connection of the 5th feed inlet 108, the other end of the first reboiler 80 and the 5th discharging Mouth 111 connects；
One end of second reboiler 90 and the connection of the 8th feed inlet 114, the other end of the second reboiler 90 and the 8th discharging Mouth 117 connects.
The material exported in 5th discharge port 111 is liquid phase material, is heated and is vaporized by the first reboiler 80, when the material Vaporization rate when reaching the first default vaporization rate, which is delivered to again in catalytic distillation tower 20, be the first mixture with The separation for mixing carbon four provides energy.Correspondingly, the material exported in the 8th discharge port 117 is also liquid phase material, pass through second The heating vaporization of reboiler 90, when the material reaches the second default vaporization rate, is delivered to recovery tower 30 for the material again and relays Continuous reaction, the separation for reaction product and inhibitor provide energy.
It in one possible implementation, include multiple reaction tubes in tube side reactor 11, multiple reaction tubes are in tube side It is triangularly arranged in reactor 11, the distance between die of two neighboring reaction tube is 100~500mm；
For each reaction tube, the height of reaction tube is 1000~15000mm, and the diameter of reaction tube is 50~250mm, instead Ying Guanzhong is filled with the second catalyst；
The both ends of reaction tube are equipped with sieve, the partial size of the screen slot size of sieve less than the second catalyst granules；The sieve of sieve It stitches twice that corresponding circulation area is not less than the corresponding cross-sectional area of outlet of reaction tube.
Wherein, the both ends of reaction tube, which are equipped with sieve, can prevent catalyst from leaking from reaction tube both ends, the screen slot ruler of sieve The very little partial size less than the second catalyst granules can prevent the second catalyst from leaking out from screen slot.The corresponding circulation of the screen slot of sieve Area is larger, can be effectively reduced reaction mass in reaction tube drop, it is ensured that reaction is normally carried out.
It should be noted is that in embodiments of the present invention, sieve can also bear entire second catalyst bed Weight, to avoid the second catalyst leakage during the reaction.Also, the maximum pressure drop of sieve is 0.1MPa.
The size of screen slot, which can according to need, to be configured and changes, in embodiments of the present invention, not to the size of screen slot Make specific limit.For example, the smallest particles diameter of the second catalyst is 0.25mm, then the size of screen slot can for 0.15~ 0.16mm；The smallest particles diameter of second catalyst is 0.23mm, then the size of screen slot can be 0.12~0.13mm.Screen slot Shape, which can according to need, to be configured and changes, for example, the size of screen slot can be round, bar shaped.In the embodiment of the present invention In, the size of screen slot is bar shaped.
First mixture and third mix carbon four namely the second reaction mass further occurrence two in tube side reactor 11 It is poly- to react, it is filled with the second catalyst in the reaction tube of tube side reactor 11, under the catalytic action of the second catalyst, second is anti- Answer material further occurrence dimerization reaction under the action of inhibitor.Since shell side reactor 12 is located at outside tube side reactor 11 Portion, therefore, the reaction heat in tube side reactor 11 can be absorbed by the first reaction mass in shell side reactor 12.Compared to phase Technology fixed bed reactors circulation in pass takes outer circulation pump and outer circulation cooler used in heat, device provided in an embodiment of the present invention Number of devices can be reduced, operating cost is reduced.
In one possible implementation, device further include: the first condenser 201, the second condenser 202, first Reflux pump 203, the second reflux pump 204, the first return tank 205 and the second return tank 206；
One end of first condenser 201 and the connection of the 4th discharge port 110, the other end of the first condenser 201 and first time Flow one end connection of tank 205, one end connection of the other end of the first return tank 205 and the first reflux pump 203, the first reflux pump 203 other end is connect with first charging aperture 101, second charging aperture 102, the 6th feed inlet 109 and the second output channel respectively；
One end of second condenser 202 and the connection of the 7th discharge port 116, the other end of the second condenser 202 and second time Flow one end connection of tank 206, one end connection of the other end of the second return tank 206 and the second reflux pump 204, the second reflux pump 204 other end is connect with first charging aperture 101 and the 9th feed inlet 115 respectively；
Wherein, the other end of the first reflux pump 203 is connected by the first regulating valve 207 and first charging aperture 101；
The other end of first reflux pump 203 is connected by the second regulating valve 208 and second charging aperture 102；
First regulating valve 207 is used to adjust the inlet amount for entering the second mixing carbon four in first charging aperture 101；
Second regulating valve 208 is used to adjust the inlet amount for entering third mixing carbon four in second charging aperture 102；
Second mixing carbon four is that mixing for first charging aperture is delivered to through the first condenser, the first return tank and the first reflux pump Close carbon four；
Third mixing carbon four is that mixing for second charging aperture is delivered to through the first condenser, the first return tank and the first reflux pump Close carbon four；
Second output channel is for exporting remaining mixing four product of carbon.
Wherein it is possible to pass through the material of the 4th discharge port 110 of circulating water condensing and the material of the 7th discharge port 116.
It can be connected by a conveyance conduit between first charging aperture 101 and the first reflux pump 203, on the conveyance conduit It is provided with the first regulating valve 207.Wherein, the first regulating valve 207 enters the second mixing carbon four in first charging aperture 101 for adjusting Inlet amount can be with when the evaporating capacity of the first reaction mass in shell side reactor 12 increases or the conversion ratio of isobutene reduces The first regulating valve 207 is tuned up, the inlet amount of the second mixing carbon four is increased；When the evaporating capacity reduction of the first reaction mass or isobutene Conversion ratio increase, generate by-product it is more when, can turn the first regulating valve 207 down, reduce the inlet amount of the second mixing carbon four.
Correspondingly, can be connected by another conveyance conduit between second charging aperture 102 and the first reflux pump 203, at this The second regulating valve 208 is provided on conveyance conduit.Wherein, the second regulating valve 208 enters the in second charging aperture 102 for adjusting The inlet amount of three mixing carbon four can be tuned up when the temperature difference of tube side reactor 11 increases or the conversion ratio of isobutene reduces Second regulating valve 208 increases the inlet amount of third mixing carbon four；When the temperature difference reduction of tube side reactor 11 or turning for isobutene Rate increases, and when generation by-product is more, can turn the second regulating valve 208 down, reduces the inlet amount of third mixing carbon four.
In one possible implementation, catalytic distillation tower 20 is mentioned including the first rectifying section, the first conversion zone and first Evaporate section；
First rectifying section includes 15~25 blocks of column plates, and the first stripping section includes 25~35 blocks of column plates；
Recovery tower 30 includes the second rectifying section and the second stripping section；
Second rectifying section includes 10~15 blocks of column plates, and the second stripping section includes 20~30 blocks of column plates.
In shell side reactor 12 unreacted gas phase mixing carbon four enter the first stripping section in catalytic distillation tower 20 the 6th~ 12 blocks of column plates；The second mixture reacted in tube side reactor 11 enters the 4th of the first stripping section in catalytic distillation tower 20 the ~10 blocks of column plates.In one possible implementation, unreacted gas phase mixing carbon four and the second mixture can enter same One block of column plate can also enter different column plates.In embodiments of the present invention, this is not especially limited.For example, working as unreacted Gas phase mixing carbon four and the second mixture when entering same column plate, the column plate can be the first stripping section the 6th block of column plate, 7th block of column plate or the 10th block of column plate.
It should be noted is that in embodiments of the present invention, the tower when serial number for the column plate being related to arranges from top to bottom The corresponding serial number of plate.
In embodiments of the present invention, by by first in the relevant technologies such as Application Number (patent) CN201711235599.7 Reactor, second reactor, first reactor outer circulation pump and outer circulation cooler, second reactor outer circulation pump and outer The multiple devices such as recirculation cooler are integrated into an equipment, i.e. shell journey superposition reactor 10, not only considerably reduce equipment And operating cost, also reduce occupation area of equipment.
The device provided in an embodiment of the present invention that diisobutylene is produced to mix carbon four as raw material, including shell journey overlapping are anti- Answer device 10, catalytic distillation tower 20 and recovery tower 30；When producing diisobutylene, pass through first reaction of the input of first charging aperture 101 Material, the first reaction mass include that the first mixing carbon four, second mixes carbon four and inhibitor, are exported by the 9th discharge port 118 Reaction product, the reaction product mainly include diisobutylene.The device mainly passes through a reactor and two tower productions two Isobutene reduces equipment used in production diisobutylene, reduces occupied area, reduce production cost and investment.
It is the method that raw material produces diisobutylene that the embodiment of the invention provides a kind of to mix carbon four, referring to Fig. 3, the party Method includes:
Step 301: the first reaction mass is delivered to the shell side reactor in shell journey superposition reactor, the first reactant Dimerization reaction occurs under the conditions of material is existing for the first catalyst, obtains the first mixture.
First reaction mass includes that the first mixing carbon four, second mixes carbon four and inhibitor, and the first mixture includes reaction Product and inhibitor mainly include diisobutylene in reaction product.
Isobutene in first mixing carbon four and the second mixing carbon four occurs dimerization reaction and generates diisobutylene, but isobutene When dimerization reaction occurs, it may also occur that the poly- reaction of trimerization reaction even four, generate trimer even tetramer, cause anti- Answering in product includes not only diisobutylene, may further include a small amount of trimer or tetramer.And in embodiments of the present invention, Inhibit isobutene to generate trimer, tetramer by inhibitor, the selectivity that isobutene generates diisobutylene is improved, to improve The yield of diisobutylene.
In one possible implementation, the first mixing carbon that temperature is 30~40 DEG C, pressure is 0.60~1.40MPa Four are inputted by the first input channel, are preheated by feed preheater, and the temperature of preheated rear first mixing carbon four is 50~70 ℃.After preheating first mixing carbon four, from catalytic distillation tower export and recycle, temperature be 45~55 DEG C, pressure 0.60 The second mixing carbon four of~1.40MPa and exported from recovery tower and recycle, temperature be 45~55 DEG C, pressure be 0.60~ The inhibitor of 1.40MPa after mixing, is entered in shell side reactor in the first input channel by first charging aperture.
Reaction pressure in shell side reactor is 0.5~0.9MPa, and reaction temperature is 70~90 DEG C, is filled in shell side reactor It is filled with the first catalyst, air speed of first catalyst in shell side reactor is 0.5~1h-1, the first mixing mixing of carbon four, second Under the catalytic action of the first catalyst dimerization reaction occurs for carbon four and inhibitor.Wherein, the first catalyst can be macropore sun Ion-exchange resin catalyst is in embodiments of the present invention not especially limited this.The air speed can be that volume space velocity can also Think mass space velocity, in embodiments of the present invention, this is not especially limited.
In embodiments of the present invention, the second mixing carbon four is Ke Xunhuanliyong, and the second mixing carbon four is recycled to shell side reactor In, the evaporating capacity of the first reaction mass or the conversion ratio of isobutene in adjustable shell side reactor.When in shell side reactor When the evaporating capacity of one reaction mass increases or the conversion ratio of isobutene reduces, the internal circulating load of the second mixing carbon four can be increased；When The evaporating capacity of the first reaction mass reduces in shell side reactor or the conversion ratio of isobutene increases, can when generation by-product is more To reduce the internal circulating load of the second mixing carbon four.Wherein, the circulation quality of the second mixing carbon four is the first mixing four mass of carbon 15%~75%.
It should be noted is that the reaction that isobutene generates diisobutylene is exothermic reaction, during the reaction, part Therefore reaction mass meeting absorbing reaction hot vapour when the first reaction mass reacts in shell side reactor, is in gas-liquid mixed shape State.In embodiments of the present invention, it is 0.5~0.9MPa by the pressure in control shell side reactor, makes reaction in relevant pressure Boiling point under carry out.Carbon four is partially mixed in reaction process, in the first reaction mass to vaporize because of absorbing reaction heat, it is unreacted Gas phase mixes carbon four and enters catalytic distillation tower from the first discharge port in shell side reactor, so that reaction temperature be made to keep permanent substantially It is fixed, and the utilization rate of catalyst can be increased substantially.Wherein, when unreacted gas phase mixing carbon four enters catalytic distillation tower, Into the 6th~12 block of column plate of the first stripping section of catalytic distillation tower.Wherein, unreacted gas phase mixing carbon four includes unreacted Gas phase first mixes carbon four and the second mixing carbon four.
First reaction mass reacts in shell side reactor, obtains the first mixture, and the first mixture is liquid phase object Material, from the second discharge port output of shell side reactor lower part, into tube side reactor, the further occurrence in tube side reactor Dimerization reaction improves the yield of diisobutylene to improve the conversion ratio of isobutene.Correspondingly, after executing the step 301, Execute step 302.
Step 302: the second reaction mass is delivered to the tube side reactor in shell journey superposition reactor, the second reactant Dimerization reaction occurs under the conditions of material is existing for the second catalyst, obtains the second mixture.
Second reaction mass includes the first mixture and third mixes carbon four, and the second mixture includes reaction product, inhibits Agent and the 4th mixing carbon four, the 4th mixing carbon four is the second reaction mass unreacted mixing carbon four in tube side reactor.
Temperature and pressure in shell side reactor is different from the temperature and pressure in tube side reactor, therefore, the first mixing Its temperature it is pre- can be cooled to first first by its pressure rise to the first preset pressure before entering tube side reactor by object If temperature.First mixture boosted and after cooling mixes carbon four with the third exported from catalytic distillation tower together from tube side The bottom of reactor enters in the reaction tube of tube side reactor, further sends out under the catalytic action of the second catalyst in reaction tube Raw dimerization reaction.
In one possible implementation, pressure of first mixture in shell side reactor is 0.5~0.9MPa, temperature Degree is 70~90 DEG C.First mixture is before entering tube side reactor, first by its pressure rise to 1.5~2.5MPa, then will Its temperature is cooled to 50~60 DEG C.
The reaction heat of the dimerization reaction occurred in tube side reactor can be inhaled by the first reaction mass in shell side reactor It receives, so as to avoid being separately provided outer circulation pump and outer circulation cooler, reduces equipment and operating cost.
In one possible implementation, the reaction pressure in tube side reactor can be 1.5~2.5MPa, reaction temperature Degree is not more than 120 DEG C, and guarantees the first mixture and third mixing carbon four namely the second reaction mass not in tube side reactor Vaporization.Wherein it is possible to pass through the reaction pressure in control tube side reactor, the first reaction mass absorbs tube side in shell side reactor Reaction heat in reactor, and increase internal circulating load the first mixture of realization and third mixing carbon four of third mixing carbon four, I.e. the second reaction mass does not vaporize in tube side reactor.
Include multiple reaction tubes in tube side reactor, is filled with the second catalyst in each reaction tube, the second catalyst exists 1~3h of air speed in reaction tube-1, and the loadings of the second catalyst are the 65%~85% of tube side reactor volume.Wherein, One mixture and third mix carbon four namely the second reaction mass the further occurrence dimerization under the catalytic action of the second catalyst Reaction.During the reaction, the second catalyst bed is in swelling state, and the second catalyst granules has irregular rotation and light Micro-disturbance, entire second catalyst bed pressure drop is small and constant, and the second catalyst bed radial temperature profile is uniform, and office is not present Portion's hot spot, to be conducive to inhibit the generation of by-product.
First catalyst and the second catalyst can be same or different.For example, the first catalyst and the second catalyst phase Together.When the first catalyst and identical the second catalyst, the first catalyst and the second catalyst can be that macroporous cation is handed over Change resin catalyst.
It should be noted is that third mixing carbon four is Ke Xunhuanliyong, third mixes the circulation of carbon four and is used as reaction mass, The conversion ratio of temperature difference or isobutene in adjustable tube side reactor.When in tube side reactor temperature difference increase or isobutyl When the conversion ratio of alkene reduces, the internal circulating load of third mixing carbon four can be increased；When in tube side reactor temperature difference reduce or it is different The conversion ratio of butylene increases, when generation by-product is more, it is possible to reduce the internal circulating load of third mixing carbon four.Wherein, third mixes The quality of carbon four is the 15%~75% of the first mixing four mass of carbon.
Step 303: respectively that the second mixture is anti-in shell side through third feed inlet, the first reaction mass from third discharge port Unreacted gas phase mixing the first discharge port of carbon four selfs for answering device to generate by vaporization is delivered to catalytic distillation through the 4th feed inlet In tower, the first reaction mass is mixed in the unreacted gas phase mixing carbon four and the 4th that shell side reactor is generated by vaporization Dimerization reaction occurs in catalytic distillation tower for carbon four, obtains third mixture.
Third mixture includes reaction product, inhibitor and the 5th mixing carbon four, and the 5th mixing carbon four is through catalytic distillation The unreacted mixing carbon four of first conversion zone of tower.
In one possible implementation, the second mixture can be delivered to through third feed inlet from third discharge port and urge Change the 4th~10 block of column plate of the first stripping section in destilling tower, the first reaction mass generates not in shell side reactor because of vaporization Reaction gas phase mixing the first discharge port of carbon four selfs through the 4th feed inlet be delivered to the first stripping section in catalytic distillation tower the 6th~ 12 blocks of column plates.Wherein, the second mixture, unreacted gas phase mixing carbon four can react simultaneously in catalytic distillation tower and It separates, dimer, the trimer etc. in inhibitor and reaction product can be discharged from the tower bottom of catalytic distillation tower, into recycling Tower.
Wherein, reaction heat can be directly used in reaction product, inhibitor and the by the catalytic distillation effect of catalytic distillation tower The separation of five mixing carbon four, to reduce energy consumption；Also, it is easy to control reaction temperature, without apparent hot localised points, is not needed It is additional to increase cooling equipment.Furthermore it is also possible to separate reaction product dimer from the first conversion zone in time, by-product is reduced Generation, improve the yield of dimer.
In one possible implementation, the first conversion zone air speed is 1~3h in catalytic distillation tower-1, reaction temperature is 60~80 DEG C, reaction pressure is 0.6~1.0MPa, can be made instead by the reaction temperature and reaction pressure that control catalytic distillation tower Product, inhibitor is answered to separate with unreacted mixing carbon four.
In one possible implementation, the 5th carbon four is mixed in catalytic distillation tower after catalytic distillation, Ke Yifen For four part mixing carbon four；
First part's mixing carbon four is back in catalytic distillation tower, and second part mixing carbon four mixes carbon four as second, It is delivered to shell side reactor, Part III mixing carbon four mixes carbon four as third, is delivered to tube side reactor, and Part IV is mixed Carbon four is closed as remaining mixing four output of products of carbon.
In alternatively possible implementation, the Partial Liquid Phase material of catalytic distillation tower tower bottom can pass through the first reboiling Device heating when reaching the first default vaporization rate, returns in catalytic distillation tower and provides energy for above-mentioned separation.First default vaporization rate It can according to need and be configured and change, such as the first default vaporization rate can be any value between 0.15~0.35.In In the embodiment of the present invention, this is not especially limited.
Step 304: reaction product and inhibitor in third mixture mix carbon four with the 5th in catalytic distillation tower and divide From, by the third mixture after separation reaction product and inhibitor be delivered to recovery tower；Reaction product and inhibitor are returning It receives and is separated in tower, reaction product is recycled as output of products, inhibitor, mixes carbon four with first and the second mixing carbon four is mixed Shell side reactor is delivered to as the first reaction mass after conjunction.
It after reaction product and inhibitor enter recovery tower, is separated in recovery tower, wherein reaction product is from recovery tower tower bottom Output, inhibitor are divided into two parts from recycling column overhead output, and a part of inhibitor is back in recovery tower, and another part inhibits Agent is used as the first reaction mass after mixing carbon four and the second mixing mixing of carbon four with first, recycles.
Include mainly dimer diisobutylene in reaction product, further includes by-product trimer, tetramer etc..What is exported is anti- Answer product that can be input to gasoline hydrodesulfurizationmethod device, as high-knock rating gasoline additive output device after adding hydrogen to be saturated； Alternatively, being input to the separation that catalytic cracking main fractionating tower carries out dimer, trimer and tetramer, wherein dimer, trimerization Object is as gasoline additive, tetramer as diesel fuel additives output device；Alternatively, being input to newly-built olefins hydrogenation dress It sets, obtains isooctane after adding hydrogen to be saturated, isooctane is as high-knock rating gasoline additive output device.In the embodiment of the present invention In, it can be selected as the case may be, this is not especially limited.
In one possible implementation, tower top temperature is 60~90 DEG C in recovery tower, and column bottom temperature is 160~190 DEG C, operating pressure is 0.5~1.0MPa.Materials at bottom of tower exports after product cooler is cooled to 40~45 DEG C.Inhibitor from return Column overhead output is received, after the second condenser is cooled to 45~55 DEG C, is boosted into the second return tank, then through the second reflux pump It is divided into two parts after 0.60~1.40MPa.
In one possible implementation, the Partial Liquid Phase material of recovery tower tower bottom can be added by the second reboiler Heat when reaching the second default vaporization rate, returns in recovery tower and provides energy for above-mentioned separation.Second default vaporization rate can basis It needs to be configured and change, such as the second default vaporization rate can be any value between 0.15~0.35.Of the invention real It applies in example, this is not especially limited.
It should be noted is that inhibitor has a very big impact the conversion ratio of isobutene.With the increasing of inhibitor Add, the ratio for covering the first catalyst or the second catalyst active center is increase accordingly, to reduce trimer, tetramer Generation, improve the yield of dimer.But excessive inhibitor can reduce the conversion ratio of isobutene, therefore, of the invention real It applies in example, the molar ratio that inhibitor mixes isobutene in carbon four with first can be 0.01~0.1:1.
Also, inhibitor, which can according to need, to be selected and is changed, and in embodiments of the present invention, is not limited specifically this It is fixed.For example, inhibitor can be the tert-butyl alcohol.
It is provided in an embodiment of the present invention with mix carbon four be raw material produce diisobutylene method, to mix carbon four as raw material Dimerization reaction occurs, inhibits the generation of by-product by inhibitor during the reaction, improves the yield of diisobutylene, and lead to It crosses diisobutylene and inhibitor separation, using diisobutylene as output of products, is added in gasoline, not only solves isobutene Outlet, also generate high-octane gasoline additive.
Technical solution of the present invention will be described in detail by specific embodiment below.
Embodiment 1
Temperature is 40 DEG C, pressure 0.80MPa, the first mixing carbon four that inlet amount is 20000kg/h pass through the first input Pipeline input, is preheated to 65 DEG C by feed preheater.First after preheating mixes carbon four, exports and follow from catalytic distillation tower Ring, temperature is 50 DEG C, pressure 0.80MPa, the second mixing carbon four that inlet amount is 10000kg/h and is exported from recovery tower And circulation, this three strands of materials of the tert-butyl alcohol that temperature is 50 DEG C, pressure 0.80MPa, inlet amount are 700kg/h is anti-as first Material is answered after mixing, into shell side reactor.It is filled with macroporous cation exchange resin catalyst in shell side reactor, Air speed of the macroporous cation exchange resin catalyst in shell side reactor is 0.75h-1.Reaction pressure in shell side reactor is 0.7MPa, reaction temperature are 72 DEG C, and reaction heat makes the first reaction mass in gas-liquid mixture phase, unreacted first mixing carbon four Enter the 8th block of column plate of the first stripping section of catalytic distillation tower from the first discharge port of shell side reactor with the second mixing carbon four.
The first mixture that temperature is 72 DEG C, pressure is 0.7MPa boosts to 1.8MPa through shell side booster, cold by shell side But device is cooled to 60 DEG C.First mixture boosted, after cooling and temperature are 50 DEG C, pressure 1.8MPa, inlet amount are Third mixing this two strands of materials of carbon four of 10000kg/h enter pipe from the bottom of tube side reactor together as the second reaction mass In journey reactor.It wherein, include 96 reaction tubes in tube side reactor, the height of every reaction tube is 14000mm, diameter is 200mm arranges from the cross section of tube side reactor in equilateral triangle.Macroporous cation exchange is filled in every reaction tube Resin catalyst, air speed of the macroporous cation exchange resin catalyst in tube side reactor are 2.0h-1.Second reaction mass exists Further occurrence dimerization reaction under the action of macroporous cation exchange resin catalyst.
The first rectifying section in catalytic distillation tower is equipped with 17 blocks of column plates, and the first conversion zone air speed is 2h-1, reaction temperature 80 DEG C, reaction pressure 0.8MPa；First stripping section is equipped with 28 blocks of column plates.Temperature is 95 DEG C, pressure 1.75MPa, inlet amount are The second mixture of 38950kg/h enters the 5th block of column plate of the first stripping section of catalytic distillation tower.In the tert-butyl alcohol and reaction product Dimer, trimer etc. are discharged from the tower bottom of catalytic distillation tower, into recovery tower.Unreacted first mixing carbon four and second mixes It closes carbon four and unreacted third mixing carbon four is moved to the first rectifying section of catalytic distillation tower, be then departed from catalytic distillation Column overhead enters the first return tank of catalytic distillation tower after the first condenser is condensed to 50 DEG C, boosts to through the first reflux pump It is divided into four part mixing carbon four after 1.9MPa；It is 10000kg/h that first part, which mixes four inlet amount of carbon, is back to catalytic distillation tower In, four inlet amount of second part mixing carbon is 10000kg/h, is delivered to shell side reactor as the second mixing carbon four, third portion Dividing mixing four inlet amount of carbon is 10000kg/h, is delivered to tube side reactor as third and mixes carbon four, Part IV mixing carbon four Inlet amount is 14200kg/h, mixes four output of products of carbon as residue.
Recovery tower column bottom temperature is 195 DEG C, operating pressure 0.85MPa, and total feed is the reaction product of 6500kg/h Enter in recovery tower simultaneously with the tert-butyl alcohol, is separated in recovery tower.The second rectifying section in recovery tower is equipped with 12 pieces of column plates, second Stripping section is equipped with 24 blocks of column plates.Tower top temperature is 87 DEG C, column bottom temperature is 166 DEG C, operating pressure 0.6MPa.Recovery tower tower bottom The reaction product load of output is 5800kg/h, and gasoline hydrodesulfurizationmethod device is entered after product cooler is cooled to 40 DEG C, As high-knock rating gasoline additive output device after adding hydrogen to be saturated.The tert-butyl alcohol is from recycling column overhead output, through the second condenser Enter the second return tank after being cooled to 50 DEG C, 0.90MPa is boosted to by the second reflux pump, is divided into two parts；First part's charging 5500kg/h containing the tert-butyl alcohol is back in recovery tower, and second part charging 700kg/h containing the tert-butyl alcohol is followed as the first reaction mass Ring is to shell side reactor.
Comparative example
Temperature is 40 DEG C, pressure 0.80MPa, the first mixing carbon four that inlet amount is 20000kg/h and temperature are 50 DEG C, The tert-butyl alcohol that pressure is 0.80MPa, inlet amount is 700kg/h is reacted in the first fixed bed reactors, reaction product one Part enters catalytic distillation tower, and another part is back to the first fixed bed reactors after removing reaction heat by heat exchanger；Through urging After changing distillation, reaction product enters the second fixed bed reactors in catalytic distillation tower, after reacting in the second fixed bed reactors It is back in catalytic distillation tower, the reaction product of catalytic distillation tower tower bottom enters extraction tower.After extracting, the anti-of column overhead is extracted Answer product that can carry out subsequent processing, the extractant and the tert-butyl alcohol of extraction tower tower bottom enter recovery tower；After recovered, the tert-butyl alcohol is returned It is back to the first fixed bed reactors.
It should be noted is that the property of material used is identical with engineering specifications in embodiment and comparative example, The product property asked is also identical.Below from engineering consumption, required equipment situation, opposite occupied area and investment etc. Embodiment and comparative example is compared, referring to table 1.
Table 1
Serial number Project Embodiment Comparative example
One Energy consumption comparison
Steam consumption 4.46t/h 4.97t/h
Recycle water consumption 267t/h 281t/h
Two Required capital equipment situation comparison
Shell journey superposition reactor 1 0
Shell side booster 1 0
Shell side cooler 1 0
First fixed bed reactors 0 1
First fixed bed reactors outer circulation pump 0 1
First fixed bed reactors outer circulation cooler 0 1
Catalytic distillation tower 1 1
Second fixed bed reactors 0 1
Recovery tower 1 1
Extraction tower 0 1
Three Occupied area comparison
Opposite occupied area 1.0 1.21
Four Investment comparison
Opposite investment 1.0 1.16
As can be seen from Table 1: steam consumption and circulation water consumption in embodiment are respectively less than comparative example.For institute With capital equipment, 1 reactor is only needed in embodiment, and comparative example needs 2 reactors；2 towers are needed in embodiment, And comparative example needs 3 towers.In addition, embodiment is again smaller than comparative example in terms of occupied area and investment.
In conclusion provided in an embodiment of the present invention to mix the device device therefor that carbon four is raw material production diisobutylene Less, occupied area is also less, and less input.
The above is merely for convenience of it will be understood by those skilled in the art that technical solution of the present invention, not to limit The present invention.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this Within the protection scope of invention.

Claims (13)

1. a kind of to mix the device that carbon four is raw material production diisobutylene, which is characterized in that described device includes: that shell journey is folded Close reactor, catalytic distillation tower and recovery tower；
The shell journey superposition reactor includes tube side reactor and shell side reactor, and the tube side reactor is located at the shell side In reactor；
The middle and upper part of shell side reactor side is equipped with first charging aperture, and the bottom of the tube side reactor is equipped with the second charging Mouthful, the middle and upper part of the shell side reactor other side is equipped with the first discharge port, and the middle and lower part of the shell side reactor other side is set There is the second discharge port, the top of the tube side reactor is equipped with third discharge port, the second charging aperture and second discharging Mouth connection；
The middle and lower part of the catalytic distillation tower side is equipped with third feed inlet and the 4th feed inlet, the catalytic distillation tower other side Lower part be equipped with the 5th feed inlet, the top of the catalytic distillation tower other side is equipped with the 6th feed inlet, the catalytic distillation tower Top be equipped with the 4th discharge port, the bottom of the catalytic distillation tower is equipped with the 5th discharge port and the 6th discharge port；Described 4th Discharge port is connect with the first charging aperture, the second charging aperture and the 6th feed inlet respectively, the 5th feed inlet It is connected with the 5th discharge port；First discharge port is connected with the 4th feed inlet, the third feed inlet and described The connection of third discharge port；
The middle and lower part of the recovery tower side is equipped with the 7th feed inlet, and the middle and lower part of the recovery tower other side is equipped with the 8th charging Mouthful, the middle and upper part of the recovery tower other side is equipped with the 9th feed inlet, and the top of the recovery tower is equipped with the 7th discharge port, described The bottom of recovery tower is equipped with the 8th discharge port and the 9th discharge port；7th feed inlet is connected with the 6th discharge port, institute The 8th feed inlet is stated to connect with the 8th discharge port, the 7th discharge port respectively with the first charging aperture and the described 9th Feed inlet connection；
For the first charging aperture for inputting the first reaction mass, the 9th discharge port is used for output-response product, and described the One reaction mass includes the first mixing carbon four, second mixing carbon four and inhibitor, the reaction product mainly include diisobutylene.
2. the apparatus according to claim 1, which is characterized in that described device further include: feed preheater and product are cooling Device；
One end of the feed preheater is connected with the first charging aperture, the other end of the feed preheater and the first input Pipeline connection；For inputting first reaction mass, the feed preheater is used for described the first input channel One mixing carbon four heats；
One end of the product cooler is connected with the 9th discharge port, the other end of the product cooler and the first output Pipeline connection；First output channel is for exporting the reaction product.
3. the apparatus according to claim 1, which is characterized in that described device further include: shell side cooler and shell side boosting Pump；
One end of the shell side booster is connected with second discharge port, the other end and the shell side of the shell side booster One end of cooler connects；
The other end of the shell side cooler is connected with the second charging aperture.
4. the apparatus according to claim 1, which is characterized in that described device further include: the first reboiler and the second reboiling Device；
One end of first reboiler is connected with the 5th feed inlet, the other end of first reboiler and the described 5th Discharge port connection；
One end of second reboiler is connected with the 8th feed inlet, the other end of second reboiler and the described 8th Discharge port connection.
5. the apparatus according to claim 1, which is characterized in that described device further include: the first condenser, the second condensation Device, the first reflux pump, the second reflux pump, the first return tank and the second return tank；
One end of first condenser is connected with the 4th discharge port, the other end of first condenser and described first One end of return tank connects, and the other end of first return tank is connected with one end of first reflux pump, and described first time Flow pump the other end respectively with the first charging aperture, the second charging aperture, the 6th feed inlet and the second output channel Connection；
One end of second condenser is connected with the 7th discharge port, the other end of second condenser and described second One end of return tank connects, and the other end of second return tank is connected with one end of second reflux pump, and described second time The other end of stream pump is connect with the first charging aperture and the 9th feed inlet respectively；
Wherein, the other end of first reflux pump is connected by the first regulating valve with the first charging aperture；
The other end of first reflux pump is connected by second regulating valve with the second charging aperture；
First regulating valve is used to adjust the inlet amount into the second mixing carbon four in the first charging aperture；
Second regulating valve is used to adjust the inlet amount into third mixing carbon four in the second charging aperture；
Described second mixes carbon four to be delivered to institute through first condenser, first return tank and first reflux pump State the mixing carbon four of first charging aperture；
The third mixing carbon four is to be delivered to through first condenser, first return tank warp and first reflux pump The mixing carbon four of the second charging aperture；
Second output channel is for exporting remaining mixing four product of carbon.
6. the apparatus according to claim 1, which is characterized in that be filled with the first catalyst in the shell side reactor；
The tube side reactor includes multiple reaction tubes, the multiple reaction tube row triangular in shape in the tube side reactor Column, the distance between die of two neighboring reaction tube are 100~500mm；
For each reaction tube, the height of the reaction tube is 1000~15000mm, the diameter of the reaction tube is 50~ 250mm is filled with the second catalyst in the reaction tube；
The both ends of the reaction tube are equipped with sieve, and the screen slot size of the sieve is less than the partial size of second catalyst granules； The corresponding circulation area of the screen slot of the sieve is not less than twice of the corresponding cross-sectional area of outlet of the reaction tube.
7. the apparatus according to claim 1, which is characterized in that the catalytic distillation tower includes the first rectifying section, first anti- Answer section and the first stripping section；
First rectifying section includes 15~25 blocks of column plates, and first stripping section includes 25~35 blocks of column plates；
The recovery tower includes the second rectifying section and the second stripping section；
Second rectifying section includes 10~15 blocks of column plates, and second stripping section includes 20~30 blocks of column plates.
8. a kind of to mix the method that carbon four is raw material production diisobutylene, which is characterized in that the described method includes:
First reaction mass is delivered to the shell side reactor in shell journey superposition reactor, first reaction mass is first Dimerization reaction occurs under the conditions of catalyst is existing, obtains the first mixture；First reaction mass includes the first mixing carbon Four, the second mixing carbon four and inhibitor；It include reaction product and the inhibitor in first mixture；The reaction product In mainly include diisobutylene；
Second reaction mass is delivered to the tube side reactor in the shell journey superposition reactor, second reaction mass exists Dimerization reaction occurs under the conditions of second catalyst is existing, obtains the second mixture；Second reaction mass includes described One mixture and third mix carbon four；Second mixture includes the reaction product, the inhibitor and the 4th mixing carbon Four, the 4th mixing carbon four is second reaction mass unreacted mixing carbon four in the tube side reactor；
It is respectively that second mixture is anti-in the shell side through third feed inlet, first reaction mass from third discharge port Unreacted gas phase mixing the first discharge port of carbon four selfs for answering device to generate by vaporization is delivered to catalytic distillation through the 4th feed inlet In tower, unreacted gas phase that first reaction mass generates due to vaporization in shell side reactor mixing carbon four and described the In the catalytic distillation tower dimerization reaction occurs for four mixing carbon four, obtains third mixture, the third mixture includes institute Reaction product, inhibitor and the 5th mixing carbon four are stated, the 5th mixing carbon four is the first reaction through the catalytic distillation tower The unreacted mixing carbon four of section；
Reaction product and inhibitor in the third mixture mix carbon four with the described 5th in the catalytic distillation tower and divide From, by the third mixture after separation reaction product and the inhibitor be delivered to recovery tower；The reaction product It being separated in the recovery tower with the inhibitor, the reaction product is recycled as output of products, the inhibitor, with It is anti-that the first mixing carbon four and the second mixing carbon four are used as first reaction mass to be delivered to the shell side after mixing Answer device.
9. according to the method described in claim 8, it is characterized in that, the method also includes:
The 5th mixing carbon four is divided for four part mixing carbon four, first part mixes carbon four and is back to the catalytic distillation tower In, second part mixing carbon four is delivered to the shell side reactor, Part III mixing carbon four as the second mixing carbon four Carbon four is mixed as the third, is delivered to the tube side reactor, Part IV mixing carbon four is produced as remaining mixing carbon four Product output.
10. according to the method described in claim 8, it is characterized in that, described respectively discharge second mixture from third Mouth is mixed through third feed inlet, first reaction mass in the unreacted gas phase that the shell side reactor is generated by vaporization The first discharge port of carbon four selfs is delivered in catalytic distillation tower through the 4th feed inlet, comprising:
Second mixture is delivered to the catalytic distillation tower first through the third feed inlet from the third discharge port 4th~10 block of column plate of stripping section；
First reaction mass is mixed into carbon four selfs institute in the unreacted gas phase that the shell side reactor is generated by vaporization State the 6th~12 block of column plate that the first discharge port is delivered to first stripping section of catalytic distillation tower through the 4th feed inlet.
11. according to the method described in claim 8, it is characterized in that, reaction pressure in the shell side reactor be 0.5~ 0.9MPa, reaction temperature are 70~90 DEG C, and air speed of first catalyst in the shell side reactor is 0.5~1h-1；
Reaction pressure in the tube side reactor is 1.5~2.5MPa, and reaction temperature is not more than 120 DEG C, second catalysis Air speed of the agent in the tube side reactor is 1~3h-1, and the loadings of second catalyst are the tube side reactor body Long-pending 65%~85%；
The first conversion zone air speed is 1~3h in the catalytic distillation tower-1, reaction temperature be 60~80 DEG C, reaction pressure be 0.6~ 1.0MPa；
In the recovery tower tower top temperature be 60~90 DEG C, column bottom temperature be 160~195 DEG C, operating pressure be 0.5~ 1.0MPa。
12. according to the method described in claim 8, it is characterized in that, the inhibitor and described first mixes isobutyl in carbon four The molar ratio of alkene is 0.01~0.1:1；
The inhibitor is the tert-butyl alcohol.
13. according to the method described in claim 8, it is characterized in that, in first reaction mass second mixing carbon four matter Amount is the 15%~75% of the first mixing four mass of carbon；
The quality of third mixing carbon four is the 15%~75% of the first mixing four mass of carbon in second reaction mass.
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